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Method for preparing bulky electron-deficient organic phosphine ligand compound

A ligand compound, large steric hindrance technology, applied in the direction of organic compound/hydride/coordination complex catalyst, organic chemistry, hydrocarbons, etc. problems, to achieve the effect of improving the coupling yield, easy availability of raw materials, and simple synthesis process

Active Publication Date: 2020-12-25
UNIV OF SCI & TECH OF CHINA
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0010] In addition, at present, the first-level alkyl and aryl groups are constructed through coupling reactions (sp 2 ) carbon-(sp 3 ) The carbon bond method is greatly affected by the ligand in terms of reactivity
For example, in realizing the coupling of primary alkyl caged germanium and aryl bromide to construct carbon (sp 2 )-carbon (sp 3 ) bond process, it was found that the yield of coupling products obtained by using common bulky electron-deficient phosphine ligands (such as the JackiePhos ligand with the following structure) was low (see: Meng-Yu Xu, Wei-Tao Jiang, Bin Xiao, et al. AlkylCarbagermatranes Enable Practical Palladium-Catalyzed sp 2 –sp 3 Cross-Coupling[J].Journal of the American Chemical Society,2019,141(18),7582-7588)

Method used

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  • Method for preparing bulky electron-deficient organic phosphine ligand compound
  • Method for preparing bulky electron-deficient organic phosphine ligand compound
  • Method for preparing bulky electron-deficient organic phosphine ligand compound

Examples

Experimental program
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Effect test

Embodiment 1

[0095] Preparation of (1,1-(dimethyl)-2-(2,4,6-triisopropylphenyl)indenyl)-bis(3,5-bis(trifluoromethyl))phenylphosphine

[0096] a) Preparation of 2-methyl-4-phenyl-3-butyn-2-ol: under an argon atmosphere, in a Schlenk bottle, successively load 50ml of anhydrous tetrahydrofuran (THF) solution, 20mmol of phenylacetylene, in At room temperature, 22 mmol of ethylmagnesium bromide in tetrahydrofuran was slowly added dropwise to phenylacetylene in tetrahydrofuran, and then the reaction solution was reacted at 40° C. for 1 hour. After cooling to room temperature, 22 mmol of acetone was slowly added, and the reaction solution was stirred at room temperature for 3 hours. After the reaction is finished, first quench the reaction with an aqueous solution of saturated ammonium chloride, then extract the reaction solution with diethyl ether, dry the organic phase with anhydrous sodium sulfate, remove the organic phase solvent under reduced pressure, and use the volume ratio of petroleum e...

Embodiment 2

[0101] Preparation of (1,1-(dimethyl)-2-(2,4,6-trimethylphenyl)indenyl)-bis(3,5-bis(trifluoromethyl))phenylphosphine

[0102] a) Preparation of 2-methyl-4-phenyl-3-butyn-2-ol: under an argon atmosphere, in a Schlenk bottle, successively load 50 ml of anhydrous tetrahydrofuran (THF) solution, 20 mmol of phenylacetylene, At room temperature, 22 mmol of methylmagnesium bromide in tetrahydrofuran was slowly added dropwise to phenylacetylene in tetrahydrofuran, and then the reaction solution was reacted at 40° C. for 1 hour. After cooling to room temperature, 22 mmol of acetone was slowly added, and the reaction solution was stirred at room temperature for 3 hours. After the reaction is finished, first quench the reaction with an aqueous solution of saturated ammonium chloride, then extract the reaction solution with diethyl ether, dry the organic phase with anhydrous sodium sulfate, remove the organic phase solvent under reduced pressure, and use the volume ratio of petroleum ethe...

Embodiment 3

[0107] Preparation of (1,1-(dimethyl)-2-(phenyl)indenyl)-bis(3,5-bis(trifluoromethyl))phenylphosphine

[0108] a) Preparation of 2-methyl-4-phenyl-3-butyn-2-ol: under an argon atmosphere, in a Schlenk bottle, successively load 50 ml of anhydrous tetrahydrofuran (THF) solution, 20 mmol of phenylacetylene, At room temperature, 22 mmol of ethylmagnesium bromide in tetrahydrofuran was slowly added dropwise to phenylacetylene in tetrahydrofuran, and then the reaction solution was reacted at 40° C. for 1 hour. After cooling to room temperature, 22 mmol of acetone was slowly added, and the reaction solution was stirred at room temperature for 3 hours. After the reaction is finished, first quench the reaction with an aqueous solution of saturated ammonium chloride, then extract the reaction solution with diethyl ether, dry the organic phase with anhydrous sodium sulfate, remove the organic phase solvent under reduced pressure, and use the volume ratio of petroleum ether to ethyl aceta...

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Abstract

The present invention relates to a novel method for preparing a large-steric-hindrance electron-deficient organic phosphine ligand compound represented by any one of the following formulae, wherein the phosphine is introduced first, the method comprises the following steps: by taking phenylacetylene as a raw material, performing a coupling reaction, and efficiently obtaining the required (1, 1-(dimethyl)-2-substituted phenyl indene (3, 5-bis (trifluoromethyl)) phenyl phosphine (5) by taking phenylacetylene as a raw material through intermediates including 2-methyl-4-phenyl-3-butyne-2-ol, 2, 3-diiodo-1, 1-dimethyl-indene and (1-iodine) indene)-bis (3-bis (3-bis (trifluoromethyl) phenyl phosphine). The novel large-steric-hindrance electron-deficient organic phosphine ligand compound is obtained through a brand-new reaction process. The organic phosphine ligand compound obtained by the invention has the advantages of stable property, stable existence in air, multiple modifiable sites, rich synthetic structure, easily available raw materials and simple synthetic method, and can be used as an important ligand in the field of palladium catalysts.

Description

technical field [0001] The invention belongs to the field of organochemical metal-catalyzed ligand synthesis and relates to large-site-blocking electron organophosphine ligand compounds, especially (1,1-(dimethyl)-2-(substituted or unsubstituted phenyl)indenyl )-a preparation method of two (3,5-bis (trifluoromethyl)) phenylphosphine ligand compounds. Background technique [0002] In the field of palladium catalysis, organophosphine ligands have always been a very important class of ligands, and its development has promoted the breakthrough of many palladium-catalyzed reactions. [0003] In 2009, Buchwald's research group discovered the macrosite in the palladium-catalyzed N-arylation reaction of secondary acyclic amides with aryl perfluorosulfonates, aryl trifluoromethanesulfonates and aryl chlorides. The electron-blocking phosphine ligand JackiePhos can efficiently catalyze this reaction (see: Jacqueline D Hicks, Alan M Hyde, Alberto Martinez Cuezva, et al. Pd-Catalyzed N-...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F9/50B01J31/24C07C1/32C07C15/107
CPCB01J31/2404B01J2531/824C07C1/325C07F9/5022C07F9/5068C07C15/107
Inventor 肖斌杨硕江伟韬
Owner UNIV OF SCI & TECH OF CHINA
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